An efficient radical-mediated carbon-sulfur bond formation reaction of vinyl halides with thiols has been developed. This reaction tolerated vinyl chloride substrates, which are barely tolerated in metal-catalyzed reactions, providing vinyl sulfide products. When vinyl iodides were used as substrates, the reactions were regulated by the solvents, yielding vinyl sulfide products in protic solvents (methanol) and alkyl sulfides in aprotic solvents (toluene).[a] Dr. Scheme 1. Examples of the reactions of vinyl halides to form vinyl sulfides.